Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions

ABSTRACT

Compositions including one or more anionic polymerization initiators and one or more additives for improving functionalizing efficiency of living polymer anions are disclosed. The present invention also provides compositions including one or more electrophiles and one or more additives for improving functionalizing efficiency of living polymer anions. Novel electrophiles and processes for improving polymer anion functionalization efficiencies are also disclosed. The additives are generally alkali metal halides or alkoxides, and the initiators are generally organs alkali metal compounds, particularly alkyl lithium compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of applicationSer. No. 09/189,664, filed Nov. 11, 1998, abandoned, incorporated byreference in its entirety, which is related to Provisional ApplicationSer. No. 60/065,858, filed Nov. 14, 1997, incorporated by reference inits entirety, and claims the benefit of its filing date under 35 USCSection 119(e).

FIELD OF THE INVENTION

This invention relates to novel compositions of an anionicpolymerization initiator and an additive which enhance functionalizationof living polymer anions; novel compositions of electrophiles and anadditive which enhance functionalization of living polymer anions; andprocesses which employ these compositions, or an additive, for improvedefficiency in the functionalization of living polymer anions.

BACKGROUND OF THE INVENTION

Polymers that contain terminal functional groups are industriallyimportant. One technique to prepare these terminally functionalizedpolymers is by reaction of a suitable electrophile with a living polymeranion. For numerous examples of end group functionalization chemistry,see Hsieh, H. L.; Quirk, R. P. Anionic Polymerization: Principles andPractical Applications; Marcel Dekker: New York, N.Y., 1996, pages261-306.

Some of these functionalization reactions are not very efficient,particularly for the preparation of telechelic polymers, due to theformation of a thick gel during the functionalization. This leads tolower capping efficiency. See, for example, U.S. Pat. No. 5,393,843,Example 1, wherein the capping efficiency was only 82%.

A recently reported terminal functionalization technique uses aprotected functionalized electrophile. For instance, Nakahama andco-workers have described the reaction of polystyryllithium with theelectrophile Br—(CH₂)₃C(OCH₃)₃, a protected carboxyl group. See Hirao,A.; Nagahama, H. Ishizone, T.; Nakahama, S. Macromolecules, 1993, 26,2145. Excellent terminal functionalization of the living anion wasachieved (>95%). Other examples of efficient functionalization withprotected functionalized electrophiles are reported in Ueda, K.; Hirao,A.; S. Nakahama, S. Macromolecules, 1990, 23, 939; Tohyama, M.; Hirao,A.; Nakahama, S. Macromol. Chem. Phys. 1996, 197, 3135, and Labeau, M.P.; Cramail, H.; Deffieux, A. Polymer International, 1996, 41, 453.

To obtain efficient functionalization, these functionalization reactionsare conducted in tetrahydrofuran (THF) at −80° C. THF, however, is anexpensive solvent, and these low-temperature conditions are notpractical on an industrial scale. In addition, efficientfunctionalization of polymer anions was only observed with expensivealkyl bromides.

SUMMARY OF THE INVENTION

The present invention provides compositions capable of increasingefficiencies in the functionalization of living polymer anions. Thecompositions include as a component one or more additives, such as analkali halide or alkali alkoxide. The inventors have unexpectedly foundthat the additives are capable of improving the efficiency of reactionsbetween polymer anions and electrophiles, as compared to similarreactions in the absence of an additive. In one aspect of the invention,the compositions include one or more additives and one or more anionicpolymerization initiators. Exemplary anionic polymerization initiatorsinclude non-functionalized and functionalized organoalkali metalinitiators. In another aspect of the invention, the compositions includeone or more additives and one or more electrophiles useful forfunctionalizing living polymers.

Processes for improving living polymer anion functionalization are alsoprovided. In this aspect of the invention, a living polymer anion isfunctionalized using a suitable electrophile in the presence of one ormore additives as described above. Higher yields of functionalizedpolymers were observed when the additive was employed. In addition, theemployment of the additive allowed the functionalization to be performedin hydrocarbon solvent at room temperature. Further, these reactionconditions are much less expensive on a commercial scale, as compared tothe prior art. The invention can also be used with a variety of monomersand/or functionalizing agents. For example, it was discovered that theless expensive, and more readily available, alkyl chlorides affordefficient functionalization when an additive is employed.

Yet another embodiment of the invention provides novel electrophiles.The novel electrophiles have the formula

wherein:

X is halogen selected from chloride, bromide and iodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, nitrogen, andmixtures thereof;

(A—R₁R₂R₃) is a protecting group, in which A is an element selected fromGroup IVa of the Periodic Table of the Elements and R₁, R₂, and R₃ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

R, R₄, and R₅ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl;

h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen; and

l is an integer from 1 to 7.

DETAILED DESCRIPTION OF THE INVENTION

Additives useful in the invention include, but are not limited to,alkali halides, such as lithium chloride, lithium bromide, lithiumiodide, sodium chloride, sodium iodide, potassium chloride, and mixturesthereof; alkali alkoxides, such as lithium t-butoxide, lithiums-butoxide, potassium t-butoxide, and mixtures thereof; and the like andmixtures thereof. The additives should be dried, prior to use.

Several factors influence the amount of additive required, such as thenature of the polymer anion; the identity of the hydrocarbon solvent;the presence of a polar additive (co-solvent); the amount of the polaradditive; the nature of the electrophile; and the identity of theadditive. An effective amount of the additive employed is from as littleas 0.01 equivalents of the electrophile, up to greater than fiveequivalents again based on the electrophile. In general, less than tenequivalents of the additive are effective for increasing the efficiencyof the functionalization reaction.

In one aspect of the invention, the compositions can include one or moreorganoalkali metal anionic polymerization initiators. Exemplary anionicpolymerization initiators include alkyllithium initiatiors representedby the formula R′—Li, wherein R′ represents an aliphatic,cycloaliphatic, or arylsubstituted aliphatic radical. Preferably, R′ isan alkyl or substituted alkyl group of 1-12 carbon atoms. Suchinitiators include, but are not limited to, methyllithium, ethyllithium,n-propyllithium, 2-propyllithium, n-butyllithium, s-butyllithium,t-butyllithium, n-hexyllithium, 2-ethylhexyllithium, and the like andmixtures thereof. As used herein, alkyllithium initiators also includedilithium initiators as known in the art. See, for example, U.S. Pat.Nos. 5,393,843 and 5,405,911. Dilithium initiators can be prepared bythe reaction of an alkyllithium reagent, such as s-butyllithium, with acompound having at least two independently polymerizable vinyl groups,such as the isomeric divinylbenzenes or isomeric diisopropenylbenzenes.

One or more functionalized organoalkali metal initiators may also beemployed in the compositions of the invention. These functionalizedinitiators have the general structure shown below:

M—Q_(n)—Z—T—(A—R₇R₈R₉)_(m)  (I)

or

wherein:

M is an alkali metal selected from the group consisting of lithium,sodium and potassium;

Q is an unsaturated hydrocarbyl group derived by incorporation of one ormore conjugated diene hydrocarbons, one or more alkenylsubstitutedaromatic compounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds into the M—Z linkage;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

A (A—R₇R₈R₉)_(m) is a protecting group in which A is an element selectedfrom Group IVa of the Periodic Table of the Elements, and R₇, R₈, and R₉are each independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

l is an integer from 1 to 7; and

m is 1 when T is oxygen or sulfur, and 2when T is nitrogen.

As used herein, the term “alkyl” refers to straight chain and branchedC1-C25 alkyl. The term “substituted alkyl” refers to C1-C25 alkylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. The term “cycloalkyl” refers to C3-C12cycloalkyl. The term “substituted cycloalkyl” refers to C3-C12cycloalkyl substituted with one or more lower C1-C10 alkyl, loweralkoxy, lower alkylthio, or lower dialkylamino. The term “aryl” refersto C5-C25 aryl having one or more aromatic rings, each of 5 or 6 carbonatoms. Multiple aryl rings may be fused, as in naphthyl or unfused, asin biphenyl. The term “substituted aryl” refers to C5-C25 arylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. Exemplary aryl and substituted arylgroups include, for example, phenyl, benzyl, and the like.

U.S. Pat. Nos. 5,496,940 and 5,527,753 disclose novel, tertiary aminoinitiators which are soluble in hydrocarbon solvents. These initiators,useful in practicing this invention, are derived fromomega-tertiary-amino-1-haloalkanes of the following general structures:

X—Z—N(A(R¹R²R³))₂

and

wherein X is defined as a halogen, preferably chlorine or bromine; Z isdefined as a branched or straight chain hydrocarbon connecting groupwhich contains 3-25 carbon atoms; A is an element selected from GroupIVa of the Periodic Table of the Elements, R¹, R² and R³ areindependently defined as hydrogen, alkyl, substituted alkyl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,aryl or substituted aryl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, or cycloalkyl and substituted cycloalkylgroups containing 5 to 12 carbon atoms, and m is an integer from 1 to 7.The process reacts selected omega-tertiary-amino-1-haloalkanes whosealkyl groups contain 3 to 25 carbon atoms, with lithium metal at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane, or aromatic reactionsolvent containing 5 to 10 carbon atoms and mixtures of such solvents.

Tertiary amino-1-haloalkanes useful in the practice of this inventioninclude, but are not limited to, 3-(N,N-dimethylamino)-1-propyl halide,3-(N,N-dimethylamino)-2-methyl-1-propyl halide,3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-dimethylamino)-1-butyl halide, 5-(N,N-dimethylamino)-1-pentylhalide, 6-(N,N-dimethylamino)-1-hexyl halide,3-(N,N-diethylamino)-1-propyl halide,3-(N,N-diethylamino)-2-methyl-1-propyl halide,3-(N,N-diethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-diethylamino)-1-butyl halide, 5-(N,N-diethylamino)-1-pentylhalide, 6-(N,N-diethylamino)-1-hexyl halide,3-(N-ethyl-N-methylamino)-1-propyl halide,3-(N-ethyl-N-methylamino)-2-methyl-1-propyl halide,3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl halide,4-(N-ethyl-N-methylamino)-1-butyl halide,5-(N-ethyl-N-methylamino)-1-pentyl halide,6-(N-ethyl-N-methylamino)-1-hexyl halide, 3-(piperidino)-1-propylhalide, 3-(piperidino)-2-methyl-1-propyl halide,3-(piperidino)-2,2-dimethyl-1-propyl halide, 4-(piperidino)-1-butylhalide, 5-(piperidino)-1-pentyl halide, 6-(piperidino)-1-hexyl halide,3-(pyrrolidino)-1-propyl halide, 3-(pyrrolidino)-2-methyl-1-propylhalide, 3-(pyrrolidino)-2,2-dimethyl-1-propyl halide,4-(pyrrolidino)-1-butyl halide, 5-(pyrrolidino)-1-pentyl halide,6-(pyrrolidino)-1-hexyl halide, 3-(hexamethyleneimino)-1-propyl halide,3-(hexamethyleneimino)-2-methyl-1-propyl halide,3-(hexamethyleneimino)-2,2-dimethyl-1-propyl halide,4-(hexamethyleneimino)-1-butyl halide, 5-(hexamethyleneimino)-1-pentylhalide, 6-(hexamethyleneimino)-1-hexyl halide,3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-propyl halide,4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-butyl halide,6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-hexyl halide,3-(N-isopropyl-N-methyl)-1-propyl halide,2-(N-isopropyl-N-methyl)-2-methyl-1-propyl halide,3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl halide, and4-(N-isopropyl-N-methyl)-1-butyl halide. The halo- or halide group isselected from chlorine and bromine.

U.S. Pat. No. 5,600,021 discloses novel monofunctional ether initiatorswhich are soluble in hydrocarbon solvents. These initiators, useful inpracticing this invention, are derived fromomega-protected-hydroxy-1-haloalkanes of the following generalstructure:

X—Z—O—(C—R¹R²R³)

wherein X is defined as a halogen, preferably chlorine or bromine; Z isa branched or straight chain hydrocarbon group which contains 3-25carbon atoms, R¹, R² and R³ are independently defined as hydrogen,alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, aryl or substituted aryl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,or cycloalkyl and substituted cycloalkyl groups containing 5 to 12carbon atoms. The process reacts selectedomega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25carbon atoms, with lithium metal at a temperature between about 35° C.and about 130° C., preferably at the reflux temperature of an alkane,cycloalkane, or aromatic reaction solvent containing 5 to 10 carbonatoms and mixtures of such solvents.

The precursor omega-protected-1-haloalkanes (halides) were prepared fromthe corresponding haloalcohol by the standard literature methods. Forexample, 3-(1,1-dimethylethoxy)-1-chloropropane was synthesized by thereaction of 3-chloro-1-propanol with 2-methylpropene according to themethod of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters,29, 1988, 2951. The method of B. Figadere, X. Franck and A. Cave,Tetrahedron Letters, 34, 1993, 5893, which involved the reaction of theappropriate alcohol with 2-methyl-2-butene catalyzed by borontrifluoride etherate is employed for the preparation of the t-amylethers. The alkoxy, alkylthio or dialkylamino substituted ethers, forexample 6-[3-(methylthio)-1-propyloxy]-1-chlorohexane, were synthesizedby reaction of the corresponding substituted alcohol, for instance3-methylthio-1-propanol, with an alpha-bromo-omega-chloroalkane, forinstance 1-bromo-6-hexane, according to the method of J. Almena, F.Foubelo and M. Yus, Tetrahedron, 51, 1995, 11883. The compound4-(methoxy)-1-chlorobutane, and the higher analogs, were synthesized bythe ring opening reaction of tetrahydrofuran with thionyl chloride andmethanol, according to the procedure of T. Ferrari and P. Vogel,SYNLETT, 1991, 233. The triphenylmethyl protected compounds, for example3-(triphenylmethoxy)-1-chloropropane, are prepared by the reaction ofthe haloalcohol with triphenylmethylchloride, according to the method ofS. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95.

Omega-hydroxy-protected-1-haloalkanes prepared in accord with thisearlier process useful in practicing this invention can include, but arenot limited to, 3-(1,1-dimethylethoxy)-1-propyl halide,3-(1,1-dimethylethoxy)-2-methyl-1-propyl halide,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylethoxy)-1-butyl halide, 5-(1,1-dimethylethoxy)-1-pentylhalide, 6-(1,1-dimethylethoxy)-1-hexyl halide,8-(1,1-dimethylethoxy)-1-octyl halide, 3-(1,1-dimethylpropoxy)-1-propylhalide, 3-(1,1-dimethylpropoxy)-2-methyl-1-propyl halide,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylpropoxy)-1-butyl halide, 5-(1,1-dimethylpropoxy)-1-pentylhalide, 6-(1,1-dimethylpropoxy)-1-hexyl halide,8-(1,1-dimethylpropoxy)-1-octyl halide, 4-(methoxy)-1-butyl halide,4-(ethoxy)-1-butyl halide, 4-(propyloxy)-1-butyl halide,4-(1-methylethoxy)-1-butyl halide,3-(triphenylmethoxy)-2,2-dimethyl-1-propyl halide,4-(triphenylmethoxy)-1-butyl halide,3-[3-(dimethylamino)-1-propyloxy]-1-propyl halide,3-[2-(dimethylamino)-1-ethoxy]-1-propyl halide,3-[2-(diethylamino)-1-ethoxy]-1propyl halide,3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyl halide,3-[2-(1-piperidino)-1-ethoxy]-1-propyl halide,3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyl halide,4-[3-(dimethylamino)-1-propyloxy]-1-butyl halide,6-[2-(1-piperidino)-1-ethoxy]-1-hexyl halide,3-[2-(methoxy)-1-ethoxy]-1-propyl halide,3-[2-(ethoxy)-1-ethoxy]-1-propyl halide,4-[2-(methoxy)-1-ethoxy]-1-butyl halide,5-[2-(ethoxy)-1-ethoxy]-1-pentyl halide,3-[3-(methylthio)-1-propyloxy]-1-propyl halide,3-[4-(methylthio)-1-butyloxy]-1-propyl halide,3-(methylthiomethoxy)-1-propyl halide,6-[3-(methylthio)-1-propyloxy]-1-hexyl halide,3-[4-(methoxy)-benzyloxy]-1-propyl halide,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyl halide,3-[2,4-(dimethoxy)-benzyloxy]-1-propyl halide,8-[4-(methoxy)-benzyloxy]-1-octyl halide,4-[4-(methylthio)-benzyloxy]-1-butyl halide,3-[4-(dimethylamino)-benzyloxy]-1-propyl halide,6-[4-(dimethylamino)-benzyloxy]-1-hexyl halide,5-(triphenylmethoxy)-1-pentyl halide, 6-(triphenylmethoxy)-1-hexylhalide, and 8-(triphenylmethoxy)-1-octyl halide. The halo- or halidegroup is selected from chlorine and bromine.

U.S. Pat. No. 5,362,699 discloses novel monofunctional silyl etherinitiators which are soluble in hydrocarbon solvents. These initiators,useful in practicing this invention, are derived fromomega-silyl-protected-hydroxy-1-haloalkanes of the following generalstructure:

X—Z—O—(Si—R¹R²R³)

wherein X is defined as a halogen, preferably chlorine or bromine; Z isa branched or straight chain hydrocarbon group which contains 3-25carbon atoms, optionally containing aryl or substituted aryl groups; andR¹, R², and R³ are independently defined as saturated and unsaturatedaliphatic and aromatic radicals, and their employment as initiators inthe anionic polymerization of olefin containing monomers in an inert,hydrocarbon solvent optionally containing a Lewis base. The processreacts selected omega-hydroxy-protected-1-haloalkanes whose alkyl groupscontain 3 to 25 carbon atoms, with lithium metal at a temperaturebetween about 25° C. and about 40° C., in an alkane, cycloalkane oraromatic reaction solvent containing 5 to 10 carbon atoms and mixturesof such solvents.

t-Butyldimethylsilyl protected compounds, for example4-(t-butyldimethylsilyloxy)-1-butylhalide, are prepared fromt-butyldimethylchlorosilane, and the corresponding halo-alcohol,according to the method described in U.S. Pat. No. 5,493,044.Omega-silyloxy-1-haloalkanes prepared in accord with this earlierprocess useful in practicing this invention can include, but are notlimited to, 3-(t-butyldimethylsilyloxy)-1-propyl halide,3-(t-butyldimethyl-silyloxy)-2-methyl-1-propyl halide,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl halide,4-(t-butyldimethylsilyloxy)-1-butyl halide,5-(t-butyldimethyl-silyloxy)-1-pentyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide,8-(t-butyldimethylsilyloxy)-1-octyl halide,3-(t-butyldiphenylylsilyloxy)-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2-methyl-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-propyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide, and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl halide. The halo- or halidegroup is selected from chlorine and bromine.

Monofunctional thioether initiators useful in the practice of thisinvention are derived from omega-protected-thio-1-haloalkanes of thefollowing general structure:

X—Z—S—(A—R¹R²R³)

wherein X is defined as a halogen, preferably chlorine or bromine; Z isa branched or straight chain hydrocarbon group which contains 3-25carbon atoms; (A—R¹R²R³) is a protecting group in which A is an elementselected from Group IVa of the Periodic Table of the Elements; R¹, R²,and R³ are independently defined as hydrogen, alkyl, substituted alkylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, aryl or substituted aryl groups containing lower alkyl, loweralkylthio, and lower dialkylamino groups, or cycloalkyl and substitutedcycloalkyl groups containing 5 to 12 carbon atoms. The process reactsselected omega-thioprotected-1-haloalkyls whose alkyl groups contain 3to 25 carbon atoms, with lithium metal at a temperature between about35° C. and about 130° C., preferably at the reflux temperature of analkane, cycloalkane or aromatic reaction solvent containing 5 to 10carbon atoms and mixtures of such solvents.

The initiator precursor, omega-thio-protected-1-haloalkanes (halides),are prepared from the corresponding halothiol by the standard literaturemethods. For example, 3-(1,1-dimethylethylthio)-1-propylchloride issynthesized by the reaction of 3-chloro-1-propanthiol with2-methylpropene according to the method of A. Alexakis, M. Gardette, andS. Colin, Tetrahedron Letters, 29, 1988, 2951. Alternatively, reactionof 1,1-dimethylethylthiol with 1-bromo-3-chloropropane and a baseaffords 3-(1,1-dimethylethylthio)-1-propylchloride. The method of B.Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893,which involved the reaction of the appropriate thiol with2-methyl-2-butene catalyzed by boron trifluoride etherate is employedfor the preparation of the t-amyl thioethers. Additionally,5-(cyclohexylthio)-1-pentylhalide and the like, can be prepared by themethod of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995,11883. This synthesis involves the reaction of the appropriate thiolwith an alkyllithium, then reaction of the lithium salt with thecorresponding alpha, omega dihalide. 3-(Methylthio)-1-propylchloride canbe prepared by chlorination of the corresponding alcohol with thionylchloride, as taught by D. F. Taber and Y. Wang, J. Org, Chem., 58, 1993,6470. Methoxymethylthio compounds, such as6-(methoxymethylthio)-1-hexylchloride, are prepared by the reaction ofthe omega-chloro-thiol with bromochloromethane, methanol, and potassiumhydroxide, by the method of F. D. Toste and I. W. J. Still, Synlett,1995, 159. t-Butyldimethylsilyl protected compounds, for example4-(t-butyldimethylsilylthio)-1-butylhalide, are prepared fromt-butyldimethylchlorosilane, and the corresponding thiol, according tothe method described in U.S. Pat. No. 5,493,044.

Omega-thio-protected 1-haloalkanes prepared in accord with this earlierprocess useful in practicing this invention can include, but are notlimited to, 3-(methylthio)-1-propylhalide,3-(methylthio)-2-methyl-1-propylhalide,3-(methylthio)-2,2-dimethyl-1-propylhalide,4-(methylthio)-1-butylhalide, 5-(methylthio)-1-pentylhalide,6-(methylthio)-1-hexylhalide, 8-(methylthio)-1-octylhalide,3-(methoxymethylthio)-1-propylhalide,3-(methoxymethylthio)-2-methyl-1-propylhalide,3-(methoxymethylthio)-2,2-dimethyl-1-propylhalide,4-(methoxymethylthio)-1-butylhalide,5-(methoxymethylthio)-1-pentylhalide,6-(methoxymethylthio)-1-hexylhalide,8-(methoxymethylthio)-1-octylhalide,3-(1,1-dimethylethylthio)-1-propylhalide,3-(1,1-dimethylethylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylethylthio)-1-butylhalide,5-(1,1-dimethylethylthio)-1-pentylhalide,6-(1,1-dimethylethylthio)-1-hexylhalide,8-(1,1-dimethylethylthio)-1-octylhalide,3-(1,1-dimethylpropylthio)-1-propylhalide,3-(1,1-dimethylpropylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylpropylthio)-1-butylhalide,5-(1,1-dimethylpropylthio)-1-pentylhalide,6-(1,1-dimethylpropylthio)-1-hexylhalide,8-(1,1-dimethylpropylthio)-1-octylhalide,3-(cyclopentylthio)-1-propylhalide,3-(cyclopentylthio)-2-methyl-1-propylhalide,3-(cyclopentylthio)-2,2-dimethyl-1-propylhalide,4-(cyclopentylthio)-1-butylhalide, 5-(cyclopentylthio)-1-pentylhalide,6-(cyclopentylthio)-1-hexylhalide, 8-(cyclopentylthio)-1-octylhalide,3-(cyclohexylthio)-1-propylhalide,3-(cyclohexylthio)-2-methyl-1-propylhalide,3-(cyclohexylthio)-2,2-dimethyl-1-propylhalide,4-(cyclohexylthio)-1-butylhalide, 5-(cyclohexylthio)-1-pentylhalide,6-(cyclohexylthio)-1-hexylhalide, 8-(cyclohexylthio)-1-octylhalide,3-(t-butyldimethylsilylthio)-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,4-(t-butyldimethylsilylthio)-1-butylhalide,6-(t-butyldimethylsilylthio)-1-hexylhalide and3-(trimethylsilylthio)-2,2-dimethyl-1-propylhalide. The halo- or halidegroup is selected from chlorine and bromine.

Functionalized organoalkali metal initiators of the following structuresmay also be employed in the compositions of the invention:

and

wherein:

M is an alkali metal;

R¹⁰ is chiral or achiral and is selected from the group consisting ofsaturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C3-C16 alkyl; and saturated and unsaturated,linear and branched, C3-C16 alkyl containing saturated or unsaturatedlower alkyl, aryl, or substituted aryl;

R¹¹ is chiral or achiral and is selected from the group consisting ofsaturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C1-C16 alkyl; saturated and unsaturated,optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;saturated and unsaturated, linear and branched, substituted C1-C16 alkylcontaining saturated or unsaturated lower alkyl, aryl, or substitutedaryl; and saturated and unsaturated substituted C3-C16 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substitutedaryl;

R¹² is a hydrocarbon connecting group or tether selected from the groupconsisting of saturated and unsaturated, linear and branched C1-C25alkyl; saturated and unsaturated C3-C25 cycloalkyl; saturated andunsaturated substituted C1-C25 alkyl containing saturated or unsaturatedlower alkyl, aryl, or substituted aryl; and saturated and unsaturatedsubstituted C3-C25 cycloalkyl containing saturated or unsaturated loweralkyl, aryl, or substituted aryl, with the proviso that the nitrogenatom and the alkali metal are separated by three or more carbon atoms;

Q is a saturated or unsaturated hydrocarbyl group derived byincorporation of one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds into the M—R¹²linkage; and

n is an integer from 1 to 5. See pending U.S. application Ser. No.09/139,222, filed Aug. 24, 1998, the entire disclosure of which ishereby incorporated by reference.

The tertiary amino initiators of this invention are prepared by reactionof selected tertiary amino halides, such as described in structure (IX),with an alkali metal selected from lithium, sodium and potassium, forexample at a temperature ranging from about 35 to 130° C.,advantageously at an elevated temperature (>40° C.), in a hydrocarbonsolvent containing five to ten carbon atoms and mixtures of suchsolvents to form an alkylorganometallic compound containing a tertiaryamine.

wherein:

X is halogen selected from the group consisting of chlorine, bromine andiodine; and R¹⁰, R¹¹, and R¹² are as defined above. These halides arecommercially available or can be prepared using techniques known in theart.

Examples of tertiary amino halides useful in the practicing thisinvention include, but are not limited to,2-(2-chloroethyl)-N-methylpiperidine,2-(2-chloroethyl)-N-ethylpiperidine,2-(2-chloroethyl)-N-propylpiperidine,2-(2-chloroethyl)-N-methylpyrrolidine,2-(2-chloroethyl)-N-ethylpyrrolidine,3-(chloromethyl)-N-methylpiperidine, 3-(chloromethyl)-N-ethylpiperidine,4-(2-chloroethyl)-N-methylpiperidine,4-(2-chloroethyl)-N-ethylpiperidine,4-(2-chloroethyl)-N-propylpiperidine,4-(chloromethyl)-N-methylpiperidine, 4-(chloromethyl)-N-ethylpiperidine,4-(chloromethyl)-N-propylpiperidine,2-(2-chloroethyl)-N-methylhexamethyleneimine,2-(2-chloroethyl)-N-methylmorpholine, and mixtures thereof.

The chain extended compounds of structure (VIII) can have greatersolubility in hydrocarbon solution than the compounds described instructure (VII). For example, the solubility of2-(2-lithioethyl)-N-methyl-piperidine in cyclohexane solution was about6 weight percent. However, when this same material was chain extendedwith two equivalents of isoprene, the solubility increased to over 28weight percent. Similar increases in solubility were observed for otherchain extended analogues.

The initiators described in structure (VIII) are prepared by reacting anorganometallic compound of the formula described in structure (VII)wherein M, R¹⁰, R¹¹, and R¹² have the meanings ascribed above, with oneor more conjugated diene hydrocarbons, one or more alkenylsubstitutedaromatic compounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds, to form an extended hydrocarbonchain between M and R¹² in structure (VIII), which extended chain isdenoted as Q_(n) in structure (VIII). The compounds of structure (VIII)are prepared by first reacting in an inert solvent a selected tertiaryamino halide (structure (IX)) with an alkali metal at a temperatureranging from about 35° C. to about 130° C., advantageously at atemperature above about 40° C., to afford an organometallic compound ofstructure (VII), which is then optionally reacted with a one or moreconjugated diene hydrocarbons, one or more alkenylsubstituted aromaticcompounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds, in a predominantly alkane,cycloalkane, or aromatic reaction solvent, which solvent contains 5 to10 carbon atoms, and mixtures of such solvents to produce an initiatorwith an extended chain or tether between the metal atom (M) and R¹² instructure (VIII) above and mixtures thereof with compounds of structure(VII).

Incorporation of Q groups into the M—R¹² linkage to form the compoundsof structure (VIII) above involves addition of compounds of structure(VII) across the carbon to carbon double bonds in compounds selectedfrom the consisting of one or more conjugated diene hydrocarbons, one ormore alkenylsubstituted aromatic compounds, or mixtures of one or moredienes with one or more alkenylsubstituted aromatic compounds to producenew carbon-lithium bonds of an allylic or benzylic nature, similar tothose found in a propagating polyalkadiene or polyarylethylene polymerchain derived by anionic initiation of the polymerization of conjugateddienes or arylethylenes. These new carbon-lithium bonds are now“activated” toward polymerization and so are much more efficient inpromoting polymerization than the precursor M—R¹² (M═Li) bondsthemselves.

In another aspect of the invention, the compositions include one or moreadditives and one or more electrophiles. The electrophiles can, forexample, include one or more functionalized alkyl halides(electrophiles). Co-pending U.S. patent application Ser. Nos.08/872,895, 08/873,220, and 08/893,951, incorporated herein byreference, detail the synthesis of telechelic and functionalized starpolymers by the reaction of living polymer anions with electrophiles ofthe following general structure:

X—Z—T—(A—R⁷R⁸R⁹)_(m)  (III)

or

wherein:

X is halogen selected from the group consisting of chloride, bromide andiodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally containing aryl or substitutedaryl groups;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

(A—R⁷R⁸R⁹)m is a protecting group in which A is an element selected fromGroup IVa of the Periodic Table of the Elements, and R⁷, R⁸, and R⁹ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

l is an integer from 1 to 7.

Examples of electrophiles of this class include, but are not limited to,3-(N,N-dimethylamino)-1-chloropropane,3-(N,N-dimethylamino)-1-bromopropane,3-(N,N-dimethylamino)-2-methyl-1-chloropropane,3-(N,N-dimethylamino)-2,2-dimethyl-1-chloropropane,4-(N,N-dimethylamino)-1-chlorobutane,5-(N,N-dimethylamino)-1-chloropentane,3-(N,N-diethylamino)-2-methyl-1-chloropropane,3-(N-ethyl-N-methylamino)-1-chloropropane,6-(N,N-dimethylamino)-1-chlorohexane,3-(N,N-diethylamino)-1-chloropropane,3-(N,N-diethylamino)-2,2-dimethyl-1-chloropropane,4-(N,N-diethylamino)-1-chlorobutane,5-(N,N-diethylamino)-1-chloropentane,6-(N,N-diethylamino)-1-chlorohexane,3-(N-ethyl-N-methylamino)-2-methyl-1-chloropropane,3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-chloropropane,4-(N-ethyl-N-methylamino)-1-chlorobutane,5-(N-ethyl-N-methylamino)-1-chloropentane,6-(N-ethyl-N-methylamino)-1-chlorohexane,3-(piperidino)-1-chloropropane, 3-(piperidino)-2-methyl-1-chloropropane,3-(piperidino)-2,2-dimethyl-1-chloropropane,4-(piperidino)-1-chlorobutane, 5-(piperidino)-1-chloropentane,6-(piperidino)-1-chlorohexane, 3-(pyrrolidino)-1-chloropropane,3-(pyrrolidino)-2-methyl-1-chloropropane,3-(pyrrolidino)-2,2-dimethyl-1-chloropropane,4-(pyrrolidino)-1-chlorobutane, 5-(pyrrolidino)-1-chloropentane,6-(pyrrolidino)-1-chlorohexane, 3-(hexamethyleneimino)-1-chloropropane,3-(hexamethyleneimino)-2-methyl-1-chloropropane,3-(hexamethyleneimino)-2,2-dimethyl-1-chloropropane,4-(hexamethyleneimino)-1-chlorobutane,5-(hexamethyleneimino)-1-chloropentane,6-(hexamethyleneimino)-1-chlorohexane,3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chloropropane,4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chlorobutane,6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chlorohexane,3-(N-isopropyl-N-methyl)-1-chloropropane,2-(N-isopropyl-N-methyl)-2-methyl-1-chloropropane,3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-chloropropane,4-(N-isopropyl-N-methyl)-1-chlorobutane,3-(1,1-dimethylethoxy)-1-chloropropane,3-(1,1-dimethylethoxy)-1-bromopropane,3-(1,1-dimethylethoxy)-2-methyl-1-chloropropane,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-chloropropane,4-(1,1-dimethylethoxy)-1-chlorobutane,5-(1,1-dimethylethoxy)-1-chloropentane,6-(1,1-dimethylethoxy)-1-chlorohexane,8-(1,1-dimethylethoxy)-1-chlorooctane,3-(1,1-dimethylpropoxy)-1-chloropropane,3-(1,1-dimethylpropoxy)-2-methyl-1-chloropropane,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-chloropropane,3-(t-butyldimethylsilyloxy)-1-chloropropane,3-(t-butyldimethyl-silyloxy)-2-methyl-1-chloropropane,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-chloropropane,4-(t-butyldimethylsilyloxy)-1-chlorobutane,4-(t-butyldimethylsilyloxy)-1-iodobutane,5-(t-butyldimethyl-silyloxy)-1-chloropentane,6-(t-butyldimethylsilyloxy)-1-chlorohexane,8-(t-butyldimethylsilyloxy)-1-chlorooctane,3-(t-butyldiphenylylsilyloxy)-1-chloropropane,3-(t-butyldiphenylylsilyloxy)-2-methyl-1-chloropropane,3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-chloropropane,6-(t-butyldimethylsilyloxy)-1-chlorohexane,3-(triethylsilyloxy)-2,2-dimethyl-1-chloropropane,3-(trimethylsilyloxy)-2,2-dimethyl-1-bromopropane and3-(trimethylsilyloxy)-2,2-dimethyl-1-chloropropane,3-(methylthio)-1-chloropropane, 3-(methylthio)-1-bromopropane,3-(methylthio)-2-methyl-1-chloropropane,3-(methylthio)-2,2-dimethyl-1-chloropropane,4-(methylthio)-1-chlorobutane, 5-(methylthio)-1-chloropentane,6-(methylthio)-1-chlorohexane, 8-(methylthio)-1-chlorooctane,3-(methoxymethylthio)-1-chloropropane,3-(methoxymethylthio)-2-methyl-1-chloropropane,3-(methoxymethylthio)-2,2-dimethyl-1-chloropropane,4-(methoxymethylthio)-1-chlorobutane,5-(methoxymethylthio)-1-chloropentane,3-(1,1-dimethylpropylthio)-1-chloropropane,3-(1,1-dimethylpropylthio)-2-methyl-1-chloropropane, and3-(t-butyldimethylsilylthio)-1-chloropropane.

Functionalizing agents, or electrophiles, of the formulaX—Z—T—(A—R⁷R⁸R⁹)_(m) or

can be prepared as described, for example, in International PublicationWO 97/16465. In addition, the electrophiles can be prepared as describedin K. Ueda, A. Hirao, and S. Nakahama, Macromolecules, 23, 939 (1990);U.S. Pat. No. 5,496,940; U.S. Pat. No. 5,600,021; U.S. Pat. No.5,362,699; A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters,29, 1988, 2951; B. Figadere, X. Franck, and A. Cave, TetrahedronLetters, 34, 1993, 5893; J. Almena, F. Foubelo, and M. Yus, Tetrahedron,51, 1995, 11883; D. F. Taber and Y. Wang, J. Org. Chem., 58, 1993, 6470;F. D. Toste and I. W. J. Still, Synlett, 1995, 159; and U.S. Pat. No.5,493,044.

Additional electrophiles that are useful in the practice of thisinvention include:

or

wherein:

X is a halogen selected from chloride, bromide and iodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, nitrogen, andmixtures thereof;

(A—R₁R₂R₃) is a protecting group, in which A is an element selected fromGroup IVa of the Periodic Table of the Elements and R₁, R₂, and R₃ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

R, R₄, and R₅ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl;

h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen;

l is an integer from 1 to 7;

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

n is 2 or 3.

Examples of electrophiles of this class include, but are not limited to,trimethyl 4-bromoorthobutyrate, trimethyl 3-chloroorthopropionate,5-chloro-2-pentanone ethylene ketal, triethyl 5-chloroorthopentanoate,N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane, and thelike and mixtures thereof.

These electrophiles can be prepared by standard literature procedures.For example, triethyl ortho-3-chloropropionate can be prepared from3-chloroprionitrile by the method of G. Casy, J. W. Patterson, and R. J.K. Taylor, Org. Syn. Coll. Vol. 8, 415 (1993). Substituted dimethyl ordiethyl dithio acetals and ketals can be prepared from the correspondinghalo aldehydes or halo ketones and methylthiol or ethylthiol and HClcatalyst, as described by H. Zinner, Chem. Ber., 83, 275 (1980). Halosubstituted 1,3-dithianes can be synthesized from the corresponding halocarbonyl compound, 1,3-propanedithiol, and boron trifluoride etheratecatalyst, as detailed by J. A. Marshall and J. L. Belletire, TetrahedronLetters, 871 (1971). Analogously, halo substituted 1,3-dithiolanes canbe synthesized from the corresponding halo carbonyl compound,1,3-ethanedithiol, and boron trifluoride etherate catalyst, as detailedby R. P. Hatch, J. Shringarpure, and S. M. Weinreb, J. Org. Chem., 43,4172 (1978). Substituted dimethyl or diethyl acetals and ketals can beprepared from the corresponding halo aldehydes or halo ketones andmethanol or ethanol and anhydrous HCl catalyst, as described by A. F. B.Cameron, J. S. Hunt, J. F. Oughton, P. A. Wilkinson, and B. M. Wilson, JChem. Soc., 3864 (1953). The method of R. A. Daignault and E. L. Eliel,Org. Syn. Col. Vol. V, 303, (1973), which involves the reaction of ahalo-substituted aldehyde or ketone with ethylene glycol, withparatolunesulfonic acid catalyst and azeotropic removal of water, can beemployed to prepare the corresponding halo-substituted 1,3-dioxolane.Halo-substituted 1,3-dioxanes can be prepared from the correspondinghalo aldehyde or ketone, 1,3-propanediol, paratoluenesulfonic acidcatalyst, with azeotropic removal of water, see J. E. Cole, W. S.Johnson, P. A. Robins, and J. Walker, J. Chem. Soc., 244 (1962), and H.Okawara, H. Nakai, and M. Ohno, Tetrahedron Letters, 23, 1087 (1982).The reaction of 2-mercaptoethanol with a halo-substituted aldehyde orketone, with zinc chloride catalyst affords the commensurate substituted1,3-oxathiolane, as reported by J. Romo, G. Rosenkranz, and C. Djerassi,J. Amer. Chem. Soc., 73, 4961 (1951) and V. K. Yadav and A. G. Fallis,Tetrahedron Letters, 29, 897 (1988). Substituted oxazolidines can besynthesized from the corresponding aminoalcohol and a halo-substitutedaldehyde or ketone, see E. P. Goldberg and H. R. Nace, J. Amer. Chem.Soc., 77, 359 (1955). In a similar fashion, the method of A. J.Carpenter and D. J. Chadwick, Tetrahedron, 41, 3803 (1985) can beemployed to generate N,N′-dimethylimidazolidines from a halo aldehyde orketone and N,N′-dimethyl-1,2-ethylenediamine. Higher homologs can beprepared from the parent halo-substituted imidazolidine viadialkylation, see J. C. Craig and R. J. Young, Org. Syn. Coll. Vol. V,88 (1973). N-3-Chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentanecan be prepared by the reaction of 3-chloropropylamine and1,1,4,4-tetramethyl-1,4-dichlorodisilethylene and an acid acceptor, seeS. Djuric, J. Venit, and P. Magnus, Tetrahedron Letters, 22, 1787(1981).

An additional class of electrophile that is useful in the practice ofthis invention is described by the general formula:

X—Z—Si—[T—(A—R₁R₂R₃)_(m)]_(n)  (VI)

wherein:

X is halogen selected from the group consisting of chloride, bromide andiodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

A is an element selected from Group IVa of the Periodic Table of theElements;

R₁, R₂, and R₃ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl;

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

n is 2or 3.

Examples of electrophiles of this class include, but are not limited to,3-chloropropyltrimethoxysilane, chloromethyltriethoxysilane,4-chlorobutyltrimethoxysilane, 3-chloropropyl-tris(dimethylamino)silane,and the like and mixtures thereof.

An additional class of electrophile that is useful in the practice ofthis invention is described by the general formula:

wherein:

Z′ is a halogen atom;

R₁₃ is selected from the group consisting of organic groups containingfrom 1 to about 12 carbon atoms and a bridging bond;

each R₁₄ is independently selected from the group consisting ofhydrogen, organic groups containing from 1 to about 12 carbon atoms anda bridging bond;

each R₁₅ is independently selected from the group consisting ofhydrogen, organic groups containing from 1 to about 12 carbon atoms;

a is an integer from 4 to about 16 and

b is an integer from 0 to about 12.

See U.S. Pat. No. 5,736,617.

Other compounds useful in functionalizing polymeric living polymersinclude, but are not limited to, alkylene oxides, such as ethyleneoxide, propylene oxide, styrene oxide, and oxetane; oxygen; sulfur;carbon dioxide; halogens such as chlorine, bromine and iodine; propargylhalides; alkenylhalosilanes and omega-alkenylarylhalosilanes, such asstyrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propanesultone; amides, including cyclic amides, such as caprolactam,N-benzylidene trimethylsilylamide, and dimethyl formamide; siliconacetals; 1,5-diazabicyclo[3.1.0]hexane; allyl halides, such as allylbromide and allyl chloride; methacryloyl chloride; amines, includingprimary, secondary, tertiary and cyclic amines, such as3-(dimethylamino)-propyl chloride andN-(benzylidene)trimethylsilylamine; epihalohydrins, such asepichlorohydrin, epibromohydrin, and epiiodohydrin, and other materialsas known in the art to be useful for terminating or end cappingpolymers. These and other useful functionalizing agents are described,for example, in U.S. Pat. Nos. 3,786,116 and 4,409,357, the entiredisclosure of each of which is incorporated herein by reference.

The impact of the additive was initially studied in thefunctionalization reaction of poly(styryl)lithium. The living polymeranion was treated with 1.5 molar equivalents of3-(N,N-dimethylamino)-1-chloropropane (Examples 1 and 2). The degree offunctionalization was determined by end group titration. The results,tabulated below, indicate that the efficiency of the functionalizationreaction increased by approximately 40% by the addition of 1.5equivalents of dry lithium chloride. Similar results were observed forthe functionalization of poly(isoprenyl) lithium (Examples 3 and 4). Thefunctionalization efficiency increased by greater than 25% when theadditive, lithium chloride, was employed.

Example Sample M_(n) MWD Additive Function 1 PS-Nme₂ 4.0 × 10³ 1.07 LiCl0.92 2 PS-Nme₂ 2.2 × 10³ 1.05 None 0.65 3 PI-Nme₂ 3.9 × 10³ 1.08 LiCl1.02 4 PI-Nme₂ 1.8 × 10³ 1.08 None 0.81

This invention also provides processes for preparing functionalizedpolymers. In the processes of the invention, an additive as describedabove is used to improve the functionalization of polymer anions withelectrophiles, including alkyl halide electrophiles. The processes forthe anionic polymerization of anionically polymerizable monomerscomprise initiating polymerization of a conjugated diene hydrocarbonmonomer, a mixture of conjugated diene monomers, an alkenylsubstitutedaromatic compound, a mixture of alkenylsubstituted aromatic compounds,or a mixture of one or more conjugated diene hydrocarbons and one ormore alkenylsubstituted aromatic compounds in a hydrocarbon or mixedhydrocarbon-polar solvent medium at a temperature of 10° C. to 150° C.with one or more initiators having the formula:

R′—Li

or

M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (I)

or

or

wherein M, Q, Z, A, R′, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², l, m, and n are asdefined above to produce an intermediate living polymer. The monomerscan be polymerized singly, sequentially or as a mixture thereof.

The intermediate living polymer is then reacted with one or moreelectrophiles, such as those described above, in the presence of anadditive, also as described above. The resultant linear or branchedmonofunctional, homotelechelic, heterotelechelic, polymer having one ormore terminal functional groups can be recovered.

The additive, or mixture of additives, can be added to the reactor atthe beginning of the polymerization, as a component of the initiatorcomposition, during the polymerization, after the polymerization butprior to the functionalization, or as a component of thefunctionalization formulation.

Monomer(s) to be anionically polymerized to form living polymer anionscan be selected from any suitable monomer capable of anionicpolymerization, including conjugated alkadienes, alkenylsubstitutedaromatic hydrocarbons, and mixtures thereof. Examples of suitableconjugated alkadienes include, but are not limited to, 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.

Examples of polymerizable alkenylsubstituted aromatic hydrocarbonsinclude, but are not limited to, styrene, alpha-methylstyrene,vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphthalene, 1,2-diphenyl-4-methyl-1-hexene andmixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl andarylalkyl derivatives thereof in which the total number of carbon atomsin the combined hydrocarbon constituents is generally not greater than18. Examples of these latter compounds include 3-methylstyrene,3,5-diethylstyrene, 4-tert-butylstyrene, 2-ethyl-4-benzylstyrene,4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene and4,5-dimethyl-1-vinylnaphthalene. U.S. Pat. No. 3,377,404, incorporatedherein by reference in its entirety, discloses suitable additionalalkenylsubstituted aromatic compounds.

The inert solvent is preferably a non-polar solvent such as ahydrocarbon, since anionic polymerization in the presence of suchnon-polar solvents is known to produce polyenes with high 1,4-contentsfrom 1,3-dienes. Inert hydrocarbon solvents useful in practicing thisinvention include but are not limited to inert liquid alkanes,cycloalkanes and aromatic solvents and mixtures thereof. Exemplaryalkanes and cycloalkanes include those containing five to 10 carbonatoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane,methylcycloheptane, octane, decane and the like and mixtures thereof.Exemplary aryl solvents include those containing six to ten carbonatoms, such as toluene, ethylbenzene, p-xylene, m-xylene, o-xylene,n-propylbenzene, isopropylbenzene, n-butylbenzene, and the like andmixtures thereof.

Polar modifiers can be added to the polymerization reaction to alter themicrostructure of the resulting polymer, i.e., increase the proportionof 1,2 (vinyl) microstructure or to promote functionalization orrandomization. Examples of polar modifiers include, but are not limitedto: diethyl ether, dibutyl ether, tetrahydrofuran (THF),2-methyltetrahydrofuran, methyl tert-butyl ether (MTBE),diazabicyclo[2.2.2]octane (DABCO), triethylamine, tri-n-butylamine,N,N,N′,N′-tetramethylethylenediamine (TMEDA), and 1,2-dimethoxyethane(glyme). The amount of the polar modifier added depends on the vinylcontent desired, the nature of the monomer, the temperature of thepolymerization, and the identity of the polar modifier.

The polymers can be optionally hydrogenated. Protecting groups whenpresent on the functionalizing agents and/or initiators can also beoptionally removed, prior to or following hydrogenation. Removal of theprotecting group(s) (deprotection) produces polymers with at least onefunctional group (e.g. oxygen, sulfur and/or nitrogen) per polymer chainon the ends of the polymer arms. The functional groups can thenparticipate in various copolymerization reactions by reaction of thefunctional groups on the ends of the polymer arms with selecteddifunctional or polyfunctional comonomers.

Deprotection can be performed either prior to or after the optionalhydrogenation of the residual unsaturation. For example, to removetert-alkyl-protected groups, the protected polymer can be mixed withAmberlyst® 15 ion exchange resin and heated at an elevated temperature,for example 150° C., until deprotection is complete.Tert-alkyl-protected groups can also be removed by reaction of thepolymer with para-toluensulfonic acid, trifluoroacetic acid, ortrimethylsilyliodide. Additional methods of deprotection of thetert-alkyl protecting groups can be found in T. W. Greene and P. G. M.Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley,N.Y., 1991, page 41.

Tert-butyldimethylsilyl protecting groups can be removed by treatment ofthe copolymer with acid, such as hydrochloric acid, acetic acid,para-toluensulfonic acid, or Dowex® 50W-X8. Alternatively, a source offluoride ions, for instance tetra-n-butylammonium fluoride, potassiumfluoride and 18-crown-6, or pyridine-hydrofluoric acid complex, can beemployed for deprotection of the tert-butyldimethylsilyl protectinggroups. Additional methods of deprotection of thetert-butyldimethylsilyl protecting groups can be found in T. W. Greeneand P. G. M. Wuts, Protective Groups in Organic Synthesis, SecondEdition, Wiley, N.Y., 1991, pages 80-83.

The progress of the deprotection reactions can be monitored byconventional analytical techniques, such as Thin Layer Chromatography(TLC), Nuclear Magnetic Resonance (NMR) spectroscopy, or InfraRed (IR)spectroscopy.

Hydrogenation techniques are described in U.S. Pat. Nos. 4,970,254,5,166,277, 5,393,843 and 5,496,898, the entire disclosure of each ofwhich is incorporated by reference. The hydrogenation of the polymer isconducted in situ, or in a suitable solvent, such as hexane, cyclohexaneor heptane. This solution is contacted with hydrogen gas in the presenceof a catalyst, such as a nickel catalyst. The hydrogenation is typicallyperformed at temperatures from 25° C. to 150° C., with a archetypalhydrogen pressure of 15 psig to 1000 psig. The progress of thishydrogenation can be monitored by InfraRed (IR) spectroscopy or NuclearMagnetic Resonance (NMR) spectroscopy. The hydrogenation reaction can beconducted until at least 90% of the aliphatic unsaturation has beensaturated. The hydrogenated polymer is then recovered by conventionalprocedures, such as removal of the catalyst with aqueous acid wash,followed by solvent removal or precipitation of the polymer.

The present invention will be further illustrated by the followingnon-limiting examples.

EXAMPLE 1 Preparation of Dimethylaminopropylpolystyrene

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified benzene (90ml.). S-butyllithium, 0.149 grams (2.3 mmole, 1.45 M in cyclohexane, 1.6mL) was then added via syringe. Purified styrene monomer (9.30 grams,89.3 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The living poly(styryl)lithiumwas then transferred into an ampoule and the known amount of residualsolution was terminated with degassed methanol from the last ampoule toobtain a base polymer sample. A second 250 ml. glass reactor wasequipped with three break-seal reagent ampoules, a sampling portattached with a Teflon® stopcock, an inlet tube fitted with a septumcap, and a magnetic stir bar. This reactor was flame sealed to a highvacuum line, and evacuated at 120° C. for 8 hours. The flask wasrefilled with dry argon, and allowed to cool to room temperature.Lithium chloride (0.133 grams, 3.14 mmols) was added to the secondreactor and dried by heating at 150° C. for an hour under vacuum. Theflask was then allowed to cool to room temperature. Thepoly(styryl)lithium (90 ml, 2.09 mmols) was transferred to one of theampoules. The second ampoule was charged with a benzene solution of3-(N,N-dimethylamino)-1-chloropropane (0.383 grams, 3.14 mmols). Thepoly(styryl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:

M_(n)=4.0×10³ g/mole

 M _(w) /M _(n)=1.07

End-group titration of the functionalized polymer indicated that thefunctionality was 0.92.

COMPARATIVE EXAMPLE Preparation of Dimethylaminopropylpolystyrene, NoAdditive

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified benzene (75ml.). S-Butyllithium, 0.251 grams (3.9 mmole, 1.45 M in cyclohexane, 2.7mL) was then added via syringe. Purified styrene monomer (8.50 grams,81.6 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The living poly(styryl)lithiumwas then transferred into an ampoule and the known amount of residualsolution was terminated with degassed methanol from the last ampoule toobtain a base polymer sample. A second 250 ml. glass reactor wasequipped with three break-seal reagent ampoules, a sampling portattached with a Teflon® stopcock, an inlet tube fitted with a septumcap, and a magnetic stir bar. This reactor was flame sealed to a highvacuum line, and evacuated at 120° C. for 8 hours. The flask wasrefilled with dry argon, and allowed to cool to room temperature. Thepoly(styryl)lithium (75 ml, 3.7 mmols) was transferred to one of theampoules. The second ampoule was charged with a benzene solution of3-(N,N-dimethylamino)-1-chloropropane (0.677 grams, 5.55 mmols). Thepoly(styryl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:

 M _(n)=2.2×10³ g/mole

M _(w) /M _(n)=1.05

End-group titration of the functionalized polymer indicated that thefunctionality was 0.65.

EXAMPLE 2 Preparation of Dimethylaminopropylpolystyrene

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified cyclohexane (90ml.). S-Butyllithium, 0.149 grams (2.3 mmole, 1.45 M in cyclohexane, 1.6mL) was then added via syringe. Purified isoprene monomer (9.00 grams,132.1 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The livingpoly(isoprenyl)lithium was then transferred into an ampoule and theknown amount of residual solution was terminated with degassed methanolfrom the last ampoule to obtain a base polymer sample. A second 250 ml.glass reactor was equipped with three break-seal reagent ampoules, asampling port attached with a Teflon® stopcock, an inlet tube fittedwith a septum cap, and a magnetic stir bar. This reactor was flamesealed to a high vacuum line, and evacuated at 120° C. for 8 hours. Theflask was refilled with dry argon, and allowed to cool to roomtemperature. Lithium chloride (0.133 grams, 3.14 mmols) was added to thesecond reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(isoprenyl)lithium (90 ml, 2.09 mmols) was transferred to one of theampoules. The second ampoule was charged with a cyclohexane solution of3-(N,N-dimethylamino)-1-chloropropane (0.383 grams, 3.14 mmols). Thepoly(isoprenyl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol and therecovered polymer was air dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:

M _(n)=3.9×10³ g/mole

M _(w) /M _(n)=1.08

End-group titration of the functionalized polymer indicated that thefunctionality was 1.02.

COMPARATIVE EXAMPLE Preparation of Dimethylaminopropylpolystyrene, NoAdditive

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified cyclohexane (75ml.). S-Butyllithium, 0.251 grams (3.9 mmole, 1.45 M in cyclohexane, 2.7mL) was then added via syringe. Purified isoprene monomer (7.10 grams,104 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The livingpoly(isoprenyl)lithium was then transferred into an ampoule and theknown amount of residual solution was terminated with degassed methanolfrom the last ampoule to obtain a base polymer sample. A second 250 ml.glass reactor was equipped with three break-seal reagent ampoules, asampling port attached with a Teflon® stopcock, an inlet tube fittedwith a septum cap, and a magnetic stir bar. This reactor was flamesealed to a high vacuum line, and evacuated at 120° C. for 8 hours. Theflask was refilled with dry argon, and allowed to cool to roomtemperature. The poly(isoprenyl)lithium (75 ml, 3.7 mmols) wastransferred to one of the ampoules. The second ampoule was charged witha cyclohexane solution of 3-(N,N-dimethylamino)-1-chloropropane (0.677grams, 5.55 mmols). The poly(isoprenyl)lithium solution and the solutionof 3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol and therecovered polymer was air dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:

M _(n)=1.8×10³ g/mole

M _(w) /M _(n)=1.08

End-group titration of the functionalized polymer indicated that thefunctionality was 0.81.

EXAMPLE 3 Preparation ofAlpha-hydroxy-omega-dimethylaminopropylpolystyrene

A 500 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified benzene (250ml.). 3-(1,1-Dimethylethoxy)-1-propyllithium, chain extended with twoequivalents of isoprene, 0.90 grams (3.5 mmole, 0.52 M in cyclohexane,6.7 mL) was then added via syringe. Purified styrene monomer (28.15grams, 89.3 mmoles) was added from a break-seal ampoule. The reactionmixture was kept for 6 hours at room temperature. The livingpoly(styryl)lithium was divided equally into three calibrated ampoulesfor reaction with the alkyl chlorides. The residual solution wasterminated with degassed methanol from the last ampoule to obtain a basepolymer sample. A second 250 ml. glass reactor was equipped with threebreak-seal reagent ampoules, a sampling port attached with a Teflon®stopcock, an inlet tube fitted with a septum cap, and a magnetic stirbar. This reactor was flame sealed to a high vacuum line, and evacuatedat 120° C. for 8 hours. The flask was refilled with dry argon, andallowed to cool to room temperature. Lithium chloride (0.041 grams, 0.97mmols) was added to the second reactor and dried by heating at 150° C.for an hour under vacuum. The flask was then allowed to cool to roomtemperature. The poly(styryl)lithium (80 ml, 0.97 mmols) was transferredto one of the ampoules. The second ampoule was charged with a benzenesolution of 3-(N,N-dimethylamino)-1-chloropropane (0.18 grams, 1.46mmoles). The poly(styryl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:

M _(n)=8.3×10³ g/mole

M _(w) /M _(n)=1.22

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃) and a dimethylaminogroup from the electrophile (δ=2.20 ppm for the —N(CH₃)₂).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylaminopropylpolystyrene polymer was isolatedand characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.98. Examination of the ¹H NMR of thisheterotelechelic polymer indicated a dimethylamino (δ=2.20 ppm for the—N(CH₃)₂) functionality of 0.91.

EXAMPLE 4 Preparation ofAlpha-hydroxy-omega-dimethylethylthiopropylpolystyrene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.041 grams, 0.97 mmols) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(styryl)lithium, prepared in Example 3 above, (80 ml, 0.97 mmols)was transferred to one of the ampoules. The second ampoule was chargedwith a benzene solution of 3-(dimethylethylthio)-1-chloropropane (0.24grams, 1.46 mmoles). The poly(styryl)lithium solution and the solutionof 3-(dimethylethylthio)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:

M _(n)=8.3×10³ g/mole

M _(w) /M _(n)=1.22

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃), and the t-butyl groupfrom the electrophile (δ=1.41 ppm for the —SC(CH₃)₃).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylethylthiopropylpolystyrene polymer wasisolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.95.

EXAMPLE 5 Preparation of Alpha-hydroxy-omega-aminopropylpolystyrene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.041 grams, 0.97 mmols) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(styryl)lithium, prepared in Example 3 above, (80 ml, 0.97 mmols)was transferred to one of the ampoules. The second ampoule was chargedwith a benzene solution ofN-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane (0.388grams, 1.46 mmoles). The poly(styryl)lithium solution and the solutionof N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane wereadded sequentially to the reactor by breaking the correspondingbreakseals. The reaction mixture was kept at room temperature for 6hours with stirring. A small sample was withdrawn with a syringe throughthe sample port for ¹H NMR analysis. Degassed methanol was then addedfrom the remaining break-seal ampoule. The resultant functionalizedpolymer solution was precipitated into a large amount of methanol. Thesilyl protecting group was removed by washing the polymer cement fivetimes with methanol and the recovered polymer was air dried for 24hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:

M _(n)=8.3×10³ g/mole

M _(w) /M _(n)=1.22

Examination of the ¹H NMR of this heterotelechelic polymer (prior todeprotection) indicated the presence of the t-butyl group from theinitiator (δ=1.17 ppm for the —OC(CH₃)₃) and indicated a siliconprotecting group (δ=0.08 ppm for the —Si(CH₃)₂—) functionality of 0.99.

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultant alpha-hydroxyl-omega-aminopropylpolystyrenepolymer was isolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 1.02.

EXAMPLE 6 Preparation ofAlpha-hydroxy-omega-dimethylaminopropylpolyisoprene

A 500 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified cyclohexane (300ml.). 3-(1,1-Dimethylethoxy)-1-propyllithium, chain extended with twoequivalents of isoprene, 1.81 grams (7.0 mmole, 0.52 M in cyclohexane,13.5 mL) was then added via syringe. Purified isoprene monomer (23.15grams, 340 mmoles) was added from a break-seal ampoule. The reactionmixture was kept for 6 hours at room temperature. The livingpoly(isoprenyl)lithium was divided equally into three calibratedampoules for reaction with the alkyl chlorides. The residual solutionwas terminated with degassed methanol from the last ampoule to obtain abase polymer sample. A second 250 ml. glass reactor was equipped withthree break-seal reagent ampoules, a sampling port attached with aTeflon® stopcock, an inlet tube fitted with a septum cap, and a magneticstir bar. This reactor was flame sealed to a high vacuum line, andevacuated at 120° C. for 8 hours. The flask was refilled with dry argon,and allowed to cool to room temperature. Lithium chloride (0.128 grams,3.03 mmoles) was added to the second reactor and dried by heating at150° C. for an hour under vacuum. The flask was then allowed to cool toroom temperature. The poly(isoprenyl)lithium (95 ml, 2.02 mmoles) wastransferred to one of the ampoules. The second ampoule was charged witha cyclohexane solution of 3-(N,N-dimethylamino)-1-chloropropane (0.37grams, 3.03 mmoles). The poly(isoprenyl)lithium solution and thesolution of 3-(N,N-dimethylamino)-1-chloropropane were addedsequentially to the reactor by breaking the corresponding breakseals.The reaction mixture was kept at room temperature for 6 hours withstirring before quenched by addition of degassed methanol from the lastbreak-seal ampoule. BHT (2,6-di-t-butyl-4-methylphenol, 0.1 wt %) wasadded to the polymer solution as an antioxidant. The resultantfunctionalized polymer solution was precipitated into a large amount ofmethanol and the recovered polymer was vacuum dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:

M _(n)=3.2×10³ g/mole

M _(w) /M _(n)=1.06

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃) and a dimethylaminogroup from the electrophile (δ=2.20 ppm for the —N(CH₃)₂).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylaminopropylpolyisoprene polymer wasisolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.92. Examination of the ¹H NMR of thisheterotelechelic polymer indicated a dimethylamino (δ=2.20 ppm for the—N(CH₃)₂) functionality of 0.90.

EXAMPLE 7 Preparation ofAlpha-hydroxy-omega-dimethylethylthiopropylpolyisoprene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.128 grams, 3.03 mmoles) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(isoprenyl)lithium, prepared in Example 6 above, (95 ml, 2.02mmoles) was transferred to one of the ampoules. The second ampoule wascharged with a cyclohexane solution of3-(dimethylethylthio)-1-chloropropane (0.50 grams, 3.03 mmoles). Thepoly(isoprenyl)lithium solution and the solution of3-(dimethylethylthio)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol and therecovered polymer was vacuum dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:

M _(n)=3.2×10³ g/mole

M _(w) /M _(n)=1.06

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃), and the t-butyl groupfrom the electrophile (δ=1.41 ppm for the —SC(CH₃)₃).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylethylthiopropylpolyisoprene polymer wasisolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.96.

EXAMPLE 8 Preparation of Alpha-hydroxy-omega-aminopropylpolyisoprene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.128 grams, 3.03 mmoles) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(isoprenyl)lithium, prepared in Example 6 above, (95 ml, 2.02mmoles) was transferred to one of the ampoules. The second ampoule wascharged with a cyclohexane solution ofN-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane (0.805grams, 3.03 mmoles). The poly(isoprenyl)lithium solution and thesolution of N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentanewere added sequentially to the reactor by breaking the correspondingbreakseals. The reaction mixture was kept at room temperature for 6hours with stirring. A small sample was withdrawn with a syringe throughthe sample port for ¹H NMR analysis. Degassed methanol was then addedfrom the remaining break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol. The silylprotecting group was removed by washing the polymer cement five timeswith methanol and the recovered polymer was vacuum dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:

M _(n)=3.2×10³ g/mole

M _(w) /M _(n)=1.06

Examination of the ¹H NMR of this heterotelechelic polymer (prior todeprotection) indicated the presence of the t-butyl group from theinitiator (δ=1.17 ppm for the —OC(CH₃)₃) and indicated a siliconprotecting group (δ=0.08 ppm for the —Si(CH₃)₂—) functionality of 1.02.

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultant alpha-hydroxyl-omega-aminopropylpolyisoprenepolymer was isolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.91.

EXAMPLE 9 Preparation of Telechelic Alpha, Omega-dihydroxy-polyisoprene

A 1000 ml. glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and is allowed to cool toroom temperature. Lithium chloride (0.64 grams, 15 mmoles) is added tothe reactor and dried by heating at 150° C. for an hour under vacuum.The flask is then allowed to cool to room temperature. The reactor ischarged with purified cyclohexane (500 ml.). S-Butyllithium, 0.64 grams(10 mmoles, 1.45 M in cyclohexane, 6.9 mL) is then added via syringe.1,3-Diisopropenylbenzene, 7.91 grams (5 mmoles) is added from a breakseal ampoule. The reactor is stirred for sixty minutes at roomtemperature, to form the dilithium initiator. Purified isoprene monomer(100 grams, 1.468 moles) is added from a break-seal ampoule. Thereaction mixture is kept for six hours at room temperature. A solutionof 3.13 grams (15 mmoles) 3-(t-rbutyldimetylsilyloxy)-1-chloropropane isadded to the reactor by breaking the corresponding breakseal. Thereaction mixture is kept at room temperature for six hours with stirringbefore quenched by addition of degassed methanol from the lastbreak-seal ampoule. BHT (2,6-di-t-butyl-4-methylphenol, 0.1 wt %) isadded to the polymer solution as an antioxidant. The resultanthomotelechelic functionalized polymer solution is precipitated into alarge amount of methanol and the recovered polymer was vacuum dried for24 hours.

The resultant base polyisoprene polymer is characterized by SEC(polyisoprene standards), and has the following properties:

M _(n)=1.05×10⁴ g/mole

M _(w) /M _(n)=1.06

Examination of the ¹H NMR indicates the presence of thet-butyldimethylsilyl group from the electrophile (δ=0.09 ppm for the—Si(CH₃)₃).

Removal of t-butyldimethylsilyl group protecting group is effected byreaction of the alpha, omega homotelechelic functionalized polymer,prepared above, with 1 N HCl in tetrahydrofuran for 6 hours underreflux. The resultant alpha, omega-dihydroxylpolyisoprene polymer isisolated and characterized.

End-group titration of the deprotected, functionalized polymer indicatesthat the functionality is 1.94.

The foregoing examples are illustrative of the present invention and arenot to be construed as limiting thereof. The invention is defined by thefollowing claims, with equivalents of the claims to be included therein.

What which is claimed is:
 1. A composition comprising one or moreanionic polymerization initiators and one or more salt additivesselected from the group consisting of sodium chloride, sodium iodide,potassium chloride, potassium t-butoxide, and mixtures thereof, forincreasing the efficiency of reactions between living polymer anions andelectrophiles, wherein the one or more additives are present in anamount between about 0.27 and about 1.5 molar equivalents of the one ormore initiators.
 2. The composition of claim 1, wherein said at leastone or more initiators is selected from the group consisting ofalkyllithium initiators, functionalized organoalkali metal initiators,and mixtures thereof.
 3. The composition of claim 2, wherein saidalkyllithium initiators are selected from the group consisting ofalkyllithium initiators of the formula R′—Li, wherein R′ is analtiphatic, cycloaliphatic, or arylsubstituted aliphatic radical, anddilithium initiators.
 4. The composition of claim 3, wherein saidalkyllithium initiators are selected from the group consisting ofmethyllithium, ethyllithium, n-propyllithium, 2-propyllithium,n-butyllithium, s-butyllithium, t-butyllithium, n-hexyllithium,2-ethylhexyllithium, and mixtures thereof.
 5. The composition of claim2, wherein said functionalized initiators are selected from the groupconsisting of compounds of the formula: M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (I)and

wherein: M is an alkali metal selected from the group consisting oflithium, sodium and potassium; Q is an unsaturated hydrocarbyl group; nis an integer from 0 to 5; Z is a branched or straight chain hydrocarbonconnecting group which contains 3-25 carbon atoms, optionallysubstituted with aryl or substituted aryl; T is selected from the groupconsisting of oxygen, sulfur, and nitrogen atoms and mixtures thereof;(A—R⁷R⁸R⁹)_(m) is a protecting group in which A is an element selectedfrom Group 14 of the Periodic Table of the Elements, and R⁷, R⁸, and R⁹are each independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl; l is an integer from 1 to 7; and m is 1 when Tis oxygen or sulfur, and 2 when T is nitrogen, and mixtures thereof. 6.The composition of claim 2, wherein said functionalized initiators areselected from the group consisting of compounds of the formula:

and

wherein: M is an alkali metal; R¹⁰ is selected from the group consistingof saturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C₃-C₁₆ alkylene; and saturated andunsaturated, linear and branched, C₃-C₁₆ alkylene containing saturatedor unsaturated lower alkyl, aryl, or substituted aryl; R¹¹ is selectedfrom the group consisting of saturated and unsaturated, linear andbranched, optionally silyl-, amino-, or oxy-substituted, C₁-C₁₆ alkyl;saturated and unsaturated, optionally silyl-, amino-, oroxy-substituted, C₃-C₁₆ cycloalkyl; saturated and unsaturated, linearand branched, substituted C₁-C₁₆ alkyl containing saturated orunsaturated lower alkyl, aryl, or substituted aryl; and saturated andunsaturated substituted C₃-C₁₆ cycloalkyl containing saturated orunsaturated lower alkyl, aryl, or substituted aryl; R¹² is a hydrocarbonconnecting group selected from the group consisting of saturated andunsaturated, linear and branched C₁-C₂₅ alkylene; saturated andunsaturated C₃-C₂₅ cycloalkylene; saturated and unsaturated substitutedC₁-C₂₅ alkylene containing saturated or unsaturated lower alkyl, aryl,and substituted aryl; and saturated and unsaturated substituted C₃-C₂₅cycloalkylene containing saturated and unsaturated lower alkyl, aryl, orsubstituted aryl, with the proviso that the nitrogen atom and the alkalimetal are separated by three or more carbon atoms; Q is a saturated orunsaturated hydrocarbyl group; n is an integer from 1 to 5; and whereinlower alkyls, aryls, and substituted aryls are defined as having shortercarbon chains than those alkyls, aryls, and substituted arylscycloalkyls, alkylenes, and cycloalkylenes to which they are connected.7. A composition comprising one or more anionic polymerizationinitiators and one or more salt additives selected from the groupconsisting of sodium chloride, sodium iodide, potassium chloride,potassium t-butoxide, lithium chloride, lithium bromide, lithium iodide,and mixtures thereof, wherein the one or more additives are present inan amount greater than 1 molar equivalent of the one or more initiators.8. The composition of claim 7, wherein said one or more additives arepresent in an amount of at least about 1.5 molar equivalent of the oneor more initiators.
 9. The composition of claim 7, wherein said at leastone or more initiators is selected from the group consisting ofalkyllithium initiators, functionalized organoalkali metal initiators,and mixtures thereof.
 10. The composition of claim 9, wherein saidalkyllithium initiators are selected from the group consisting ofalkyllithium initiators of the formula R′—Li, wherein R′ is analiphatic, cycloaliphatic, or arylsubstituted aliphatic radical, anddilithium initiators.
 11. The composition of claim 10, wherein saidalkyllithium initiators are selected from the group consisting ofmethyllithium, ethyllithium, n-propyllithium, 2-propyllithium,n-butyllithium, s-butyllithium, t-butyllithium, n-hexyllithium,2-ethylhexyllithium, and mixtures thereof.
 12. The composition of claim9, wherein said functionalized organoalkali metal initiators areselected from the group consisting of compounds of the formula:M—Q_(n)—Z—T—(A—R⁷R⁸R9)_(m)  (I) and

wherein: M is an alkali metal selected from the group consisting oflithium, sodium and potassium; Q is an unsaturated hydrocarbyl group; nis an integer from 0 to 5; Z is a branched or straight chain hydrocarbonconnecting group which contains 3-25 carbon atoms, optionallysubstituted with aryl or substituted aryl; T is selected from the groupconsisting of oxygen atoms, sulfur atoms, nitrogen atoms and mixturesthereof; (A—R⁷R⁸R⁹)_(m) is a protecting group in which A is an elementselected from Group 14 of the Periodic Table of the Elements, and R⁷,R⁸, and R⁹ are each independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl,and substituted cycloalkyl; l is an integer from 1 to 7; and m is 1 whenT is oxygen or sulfur, and 2 when T is nitrogen or a mixture of atomsselected from the group consisting of oxygen, sulfur, and nitrogen. 13.The composition of claim 9, wherein said functionalized initiators areselected from the group consisting of compounds of the formula:

and

wherein: M is an alkali metal; R¹⁰ is selected from the group consistingof saturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C₃-C₁₆ alkylene; and saturated andunsaturated, linear and branched, C₃-C₁₆ alkylene containing saturatedor unsaturated lower alkyl, aryl, or substituted aryl; R¹¹ is selectedfrom the group consisting of saturated and unsaturated, linear andbranched, optionally silyl-, amino-, or oxy-substituted, C₁-C₁₆ alkyl;saturated and unsaturated, optionally silyl-, amino-, oroxy-substituted, C₃-C₁₆ cycloalkyl; saturated and unsaturated, linearand branched, substituted C₁-C₁₆ alkyl containing saturated orunsaturated lower alkyl, aryl, or substituted aryl; and saturated andunsaturated substituted C₃-C₁₆ cycloalkyl containing saturated orunsaturated lower alkyl, aryl, or substituted aryl; R¹² is a hydrocarbonconnecting group selected from the group consisting of saturated andunsaturated, linear and branched C₁-C₂₅ alkylene; saturated andunsaturated C₃-C₂₅ cycloalkylene; saturated and unsaturated substitutedC₁-C₂₅ alkylene containing saturated or unsaturated lower alkyl, aryl,and substituted aryl; and saturated and unsaturated substituted C₃-C₂₅cycloalkylene containing saturated and unsaturated lower alkyl, aryl, orsubstituted aryl, with the proviso that the nitrogen atom and the alkalimetal are separated by three or more carbon atoms; Q is a saturated orunsaturated hydrocarbyl group; n is an integer from 1 to 5; and whereinlower alkyls, aryls, and substituted aryls are defined as having shortercarbon chains than those alkyls, cycloalkyls, alkylenes, andcycloalkylenes to which they are connected.
 14. A composition of claim7, wherein said one or more anionic polymerization initiators comprisen-butyllithium and said one or more additives comprise lithium chloride.15. The composition of claim 14, wherein n-butyllithium is present in anamount greater than 1 molar equivalent of lithium chloride.
 16. Thecomposition of claim 14, wherein n-butyllithium is present in an amountof at least about 1.5 molar equivalent of lithium chloride.
 17. Acomposition comprising one or more anionic polymerization alkyllithiuminitiators of the formula R′—Li, wherein R′ is an aliphatic,cycloaliphatic, or arylsubstituted aliphatic radical, and dilithiuminitiators and one or more salt additives selected from the groupconsisting of sodium chloride, sodium iodide, potassium chloride,potassium t-butoxide, lithium chloride, lithium bromide, lithium iodide,and mixtures thereof, wherein the one or more additives are present inan amount greater than 1 molar equivalent of the one or morealkyllithium initiators.
 18. The composition of claim 17, wherein saidone or more additives are present in an amount of at least about 1.5molar equivalent of the one or more alkyllithium initiators.